Direct alkoxylation of bio-oil

ABSTRACT

An alkoxylated bio-oil composition is provided. The alkoxylated bio-oil composition may include an alkoxylated bio-oil prepared from an alkoxylation of dewatered bio-oil. A method for preparing an alkoxylated bio-oil composition is provided. A copolymer composition is provided. The copolymer composition may include an alkoxylated bio-oil copolymer unit. A method for preparing a copolymer composition is provided.

RELATED APPLICATION

This is a divisional application which claims the benefit of U.S. patentapplication Ser. No. 15/619,707 titled “DIRECT ALKOXYLATION OF BIO OIL”,filed on Jun. 12, 2017, which claims priority and the benefit of U.S.Provisional Patent Application 62/348,863, filed Jun. 11, 2016. Theentire contents of the above-identified applications are incorporatedherein by reference.

BACKGROUND

Biomass such as, for example, lignocellulosic substances (e.g., wood),may be subjected to pyrolysis to create a hot pyrolysis vapor. Bio-oilmay be extracted from the hot pyrolysis vapor. Bio-oil from pyrolysis ofwood may contain a mixture of water, organic acids, alcohols, aldehydes,phenols, and sugar derivatives. The production and availability ofbio-oil and bio-oil derivatives may provide a ready starting materialfor many chemical transformations.

The present application appreciates that developing bio-oil and bio-oilderivatives may be a challenging endeavor.

SUMMARY

In one embodiment, a method for preparing an alkoxylated bio-oilcomposition is provided. The method may include providing a dewateredbio-oil. The method may include contacting the dewatered bio-oil to analkoxylation reagent. The method may include reaction conditionseffective to form an alkoxylated bio-oil.

In one embodiment, an alkoxylated bio-oil composition is provided. Thealkoxylated bio-oil composition may include an alkoxylated bio-oil. Thealkoxylated bio-oil may be derived from a dewatered bio-oil. Thealkoxylated bio-oil composition may include a free alkylene glycol inless than about 40 wt % compared to an amount of the alkoxylatedbio-oil.

In one embodiment, a method for preparing a copolymer composition isprovided. The method may include providing a polymerization precursormixture. The polymerization precursor mixture may include a crosslinkingreagent. The crosslinking reagent may be configured to form a copolymerin combination with an alkoxylated bio-oil. The alkoxylated bio-oilcomposition may include an alkoxylated bio-oil. The method may includereacting an alkoxylated bio-oil composition with the polymerizationprecursor mixture. The alkoxylated bio-oil composition may include thealkoxylated bio-oil. The method may include reaction conditionseffective to form the copolymer composition.

In one embodiment, a copolymer composition is provided. The copolymercomposition may include a copolymer. The copolymer may include analkoxylated bio-oil unit. The alkoxylated bio-oil unit may be derivedfrom an alkoxylated bio-oil composition including an alkoxylatedbio-oil. The copolymer may include a cross-linking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecross-linking unit may be effective to crosslink more than onealkoxylated bio-oil unit to form the copolymer.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures, which are incorporated in and constitute apart of the specification, illustrate example methods and compositions,and are used merely to illustrate example embodiments.

FIG. 1 is a flow diagram illustrating an example method for preparing analkoxylated bio-oil composition.

FIG. 2 is a flow diagram illustrating an example method for preparing acopolymer composition.

FIG. 3 is a table illustrating resulting properties of alkoxylatedbio-oils from direct alkoxylation of dewatered bio-oils with propyleneglycol; and resulting properties of polyurethane foams prepared from thealkoxylated bio-oils.

FIG. 4 is a table illustrating a reference formulation for thepreparation of polyurethane foams.

FIG. 5 is a table illustrating a general formulation for the preparationof polyurethane foams.

FIG. 6 is a graph illustrating a correlation between compressivestrength and density of reference polyurethane foams.

DETAILED DESCRIPTION

Bio-oil produced from the pyrolysis of wood or other lignocellulosicbiomass may contain many components, including water, alcohols, organicacids, phenols, and sugars. Bio-oil produced by pyrolysis may includebio-oil polyols. Functionalized bio-oils may provide added value, forexample, as replacement polyol reagents in polymerizations for formingpolyesters, polyurethanes, copolymers, phenolic resins, hot meltadhesive compositions, and the like. Producing functionalized bio-oilsmay include alkoxylation of bio oils to provide alkoxylated bio-oils. Itmay be desirable to avoid water in alkoxylation reactions, as the watermay react with alkoxylation reagents, e.g., propylene oxide, and lead toformation of undesirable corresponding free alkylene glycols, e.g.,mono- or polyalkylene glycols. The presence of free alkylene glycols inalkoxylated bio-oil compositions may introduce obstacles in generatingmaterials with desired properties.

FIG. 1 is a flow diagram illustrating an example method 100 forpreparing an alkoxylated bio-oil composition.

In various embodiments, method 100 may include 102 providing a dewateredbio-oil. Method 100 may include 104 contacting the dewatered bio-oil toan alkoxylation reagent. Method 100 may include reaction conditionseffective to form an alkoxylated bio-oil.

Method 100 may include the dewatered bio-oil produced from a bio-oil.The bio-oil may be produced from pyrolysis of a biomass. The bio-oil maybe produced from catalytic pyrolysis of a biomass. The biomass mayoriginate from wood or other lignocellulosic-containing biomass.

The dewatered bio-oil may be produced by a dewatering step of a bio-oil.The bio-oil may be produced by pyrolysis of biomass. Additionally oralternatively, the bio-oil may be a catalytic bio-oil produced bycatalytic pyrolysis of biomass. Biomass may include, for example,lignin, cellulose, or lignocelluloses or mixtures thereof.

The dewatering step may include heating a bio-oil containing water to atemperature of at least 100° C. (distillation). The dewatering step mayinclude heating a bio-oil containing water to a temperature less than100° C. under reduced pressure (vacuum distillation). The dewateringstep may further include condensing a water vapor in a containerseparate from the bio-oil in order to provide the dewatered bio-oil. Thedewatering step may include cooling a bio-oil containing water to atemperature less than 0° C. under reduced pressure (freeze drying).

The dewatering step may include contacting a bio-oil containing waterwith a composition. The composition may be effective to form anazeotrope with water. The composition may include, for example, benzene,toluene, ethanol, and the like. The dewatering step may include heatingthe bio-oil containing water and the composition to a temperatureeffective to co-distill the water and the composition. The dewateringstep may include heating the bio-oil containing water and thecomposition to a temperature under a reduced pressure effective toco-distill the water and the composition. The dewatering step mayfurther include condensing a water vapor and a composition vapor in acontainer separate from the bio-oil in order to provide the dewateredbio-oil.

The dewatering step may include allowing the bio-oil containing water tostand open to the atmosphere (evaporation). The dewatering step mayfurther include heating the bio-oil containing water while being open tothe atmosphere. The dewatering step may further include passing a streamof gas over the surface of the bio-oil containing water to aidevaporation. The dewatering step may further include bubbling a gasthrough the bio-oil containing water to aid evaporation. The gas mayinclude, for example, air, nitrogen, argon, and the like.

The dewatering step may include immersing an adsorbent medium in thebio-oil containing water for a period of time and further filtering thebio-oil to remove the adsorbent medium. The dewatering step may includepassing a bio-oil over an adsorbent medium. The dewatering step mayinclude housing the bio-oil containing water in a container including acompartmentalized adsorbent medium chamber separate from the bio-oilcontaining water. The adsorbent medium may include a desiccant or dryingagent, such as sodium sulfate, magnesium sulfate, calcium sulfate, andthe like. The adsorbent medium may include molecular sieves.

The dewatering step may include separating water from a bio-oil bycentrifugal force (centrifugation). The dewatered bio-oil may further beremoved by decantation.

The dewatered bio-oil may be produced by a dewatering step of a bio-oil.The dewatering step may include washing the bio-oil containing waterwith a saturated aqueous solution of, for example, sodium chloride.

The dewatered bio-oil of method 100 may include an amount of water inless than about 3 wt % compared to an amount of the dewatered bio-oil.The dewatered bio-oil of method 100 may include an amount of water inless than about 2 wt %. The dewatered bio-oil of method 100 may includean amount of water in less than about 1.5 wt %. The dewatered bio-oil ofmethod 100 may include an amount of water in wt % of less than about oneor more of: 0.5, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8,3.0, 3.2, and 3.5. The dewatered bio-oil of method 100 may include anamount of water in wt % between any of the preceding values, forexample, between about 1.4 and about 1.6, or between about 1.8 and about2.4. The dewatered bio-oil of method 100 may include an amount of waterin more than about 10 wt %. The dewatered bio-oil of method 100 mayinclude an amount of water up to about 30 wt %. The dewatered bio-oil ofmethod 100 may include an amount of water in wt % of less than about oneor more of: 30, 25, 20, 15, 10, 5, 4, 3, 2, and 1. The dewatered bio-oilof method 100 may include an amount of water in wt % between any of thepreceding values, for example, between about 3 and about 4, or betweenabout 5 and about 15. The percentage of water present in the dewateredbio-oil may be determined by Karl Fischer (KF) titration.

The alkoxylation reagent of method 100 may include an epoxide, commonlyknown as an oxirane or an alkylene oxide. The alkoxylation reagent mayinclude ethylene oxide. The alkoxylation reagent may include ethyleneoxide substituted with a linear or branched C₁-C₆ alkyl, such aspropylene oxide. The alkoxylation reagent may include ethylene oxidesubstituted with a C₃-C₆ cycloalkyl group, such as 2-cyclohexyloxiraneor 7-oxabicyclo[4.1.0]heptane. The alkoxylation reagent may includeethylene oxide substituted with a C₄-C₁₀ aryl or heteroaryl group, suchas 2-phenyloxirane. The alkoxylation reagent may include one or more ofa linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.

The alkoxylation reagent of method 100 may include a cyclic carbonate.The cyclic carbonate may include ethylene carbonate. The cycliccarbonate may include trimethylene carbonate. The cyclic carbonate maybe substituted with a linear or branched C₁-C₆ alkyl, such as propylenecarbonate. The cyclic carbonate may be substituted with a C₃-C₆cycloalkyl group. The cyclic carbonate may be substituted with a C₄-C₁₀aryl or heteroaryl group. The cyclic carbonate may include one or moreof a linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and aC₄-C₁₀ aryl or heteroaryl group.

The alkoxylation reagent in method 100 may be present in an amountgreater than about 10 wt % compared to an amount of dewatered bio-oil.The alkoxylation reagent in method 100 may be present in an amount lessthan about 50 wt % compared to an amount of dewatered bio-oil. Thealkoxylation reagent in method 100 may be present in an amount in wt %compared to an amount of dewatered bio-oil of at least about one or moreof: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55,60, 65, 70, 75, 80, 85, 90, 95, and 100, or a range between any two ofthe preceding values, for example, between about 5% and about 70%. Thealkoxylation reagent in method 100 may be present in an amount in wt %compared to an amount of dewatered bio-oil between any of the precedingvalues, for example, between about 25 and about 45, or between about 10and about 30. The alkoxylation reagent in method 100 may be present inabout 45 wt % compared to the amount of dewatered bio-oil. Thealkoxylation reagent in method 100 may be present in an amount greaterthan 50 wt % compared to an amount of dewatered bio-oil. Thealkoxylation reagent in method 100 may be present in an amount greaterthan 100 wt % compared to an amount of dewatered bio-oil.

Method 100 may include reaction conditions including the presence of thepromoter. The promoter may include a base. The base may include analkali metal hydroxide. The alkali metal hydroxide may include sodiumhydroxide, potassium hydroxide, cesium hydroxide, and the like. Thepromoter may include an alkali metal hydride, such as sodium hydride,potassium hydride, and the like. Alternatively, the promoter may includea Brønsted acid, such as acetic acid, p-toluene sulfonic acid, or thelike. The promoter may include a Lewis acid, such as compounds based onboron, aluminum, a lanthanide, or the like.

The promoter may be present in a sub-stoichiometric amount (catalytic).The promoter in method 100 may be present in an amount less than about 1wt % compared to an amount of dewatered bio-oil. The promoter may bepresent in an amount in wt % compared to an amount of dewatered bio-oilof at least about one or more of: 0.002, 0.005, 0.008, 0.01, 0.05, 0.1,0.5, 1.0, 1.5, 2, 3, 4, 5, 7, 10, 15, and 20. The promoter may bepresent in an amount in wt % compared to an amount of dewatered bio-oilbetween any of the preceding values, for example, between about 0.002and about 0.005, or between about 0.05 and about 1.5. The promoter maybe present in an amount greater than about 20 wt % compared to an amountof dewatered bio-oil. The promoter may be present in an amount greaterthan or equal to about 100 wt %.

Method 100 may further include first contacting the dewatered bio-oilwith a promoter. Method 100 may include allowing the dewatered bio-oiland the promoter to react for a period of time prior to contacting thedewatered bio-oil with the alkoxylation reagent. Method 100 may furtherinclude heating the dewatered bio-oil and the promoter at a temperaturein ° C. of one or more of: 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, 90, and 100. Method 100 may include heating the dewateredbio-oil and the promoter at a temperature in ° C. between any of thepreceding values, for example, between about 60 and about 70, or betweenabout 90 and about 100. Method 100 may include heating the dewateredbio-oil and the promoter at a temperature greater than 100° C. Method100 may optionally include heating the dewatered bio-oil and thepromoter at a temperature under reduced pressure. Method 100 may includea reduced pressure in torr of at least about one or more of: 700, 650,600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, and5. Method 100 may include a reduced pressure in Torr between any of thepreceding values, for example, between about 150 and about 100, orbetween about 350 and about 200.

In many embodiments, water may be formed while contacting the dewateredbio-oil to the promoter, for example, if the promoter was an alkalimetal hydroxide or Brønstad acid. Method 100 may include continualremoval of generated water throughout a reaction between the dewateredbio-oil and the promoter prior to contacting the dewatered bio-oil withthe alkoxylation reagent. Method 100 may optionally include condensing awater vapor into a container separate from the dewatered bio-oil and thepromoter. In many embodiments, the alkoxylation reagent may be added tothe dewatered bio-oil and the promoter after the dewatered bio-oil andthe promoter have been in contact for a period of time. In someembodiments, a second charge of promoter may be added to the dewateredbio-oil and the alkoxylation reagent after the dewatered bio-oil and afirst charge of the promoter have been in contact for a period of time.In other embodiments, the dewatered bio-oil, the promoter, and thealkoxylation reagent are added at once.

Method 100 may include reaction conditions effective to form thealkoxylated bio-oil. Method 100 may include a reaction temperature of atleast about 50° C. Method 100 may include a reaction temperature in ° C.of at least about one or more of: 50, 70, 90, 100, 110, 120, 130, 140,150, 160, 170, and 180. Method 100 may include a reaction temperature in° C. between any of the preceding values, for example, between about 110and about 150, or between about 130 and about 140. Method 100 mayinclude a reaction temperature of less than about 50° C. Method 100 mayinclude a reaction temperature of greater than 180° C. Method 100 mayinclude a reaction temperature that varies throughout the progress ofthe reaction, for example, the reaction may begin at a temperature ofless than about 25° C. for a period of time, and gradually increase to atemperature of greater than about 100° C.

Method 100 may include reaction conditions effective to form thealkoxylated bio-oil. Method 100 may include a reaction pressure inpounds per square inch of at least about one or more of: 0, 50, 100,150, 200, 250, 300, 350, 400, 450, 500, 550, and 600. Method 100 mayinclude a reaction pressure in pounds per square inch between any of thepreceding values, for example, between about 50 and about 100, orbetween about 150 and about 300. Method 100 may include an autoclavereactor or a bomb reactor.

Method 100 may include reaction conditions effective to from thealkoxylated bio-oil. Method 100 may include microwave radiation. Method100 may include use of a microwave reactor.

Method 100 may include reaction conditions effective to form thealkoxylated bio-oil. Method 100 may include a reaction time of at leastabout 2 h. Method 100 may include a reaction time of at least about 4 h.Method 100 may include a reaction time in minutes of at least about oneor more of: 10, 30, 60, 90, 120, 150, 180, 210, 240, 270, and 300.Method 100 may include a reaction time in minutes between any of thepreceding values, for example, between about 30 and about 90, or betweenabout 180 and about 240. Method 100 may include a reaction time ofgreater than 300 min.

Method 100 may include reaction conditions effective to form analkoxylated bio-oil. Method 100 may include reaction conditions tominimize the formation of a free alkylene glycol. The free alkyleneglycol may result from reaction between water and the alkoxylationreagent. Method 100 may include an amount of the free alkylene glycolproduced in less than about 10 wt % compared to the amount ofalkoxylated bio-oil. Method 100 may include an amount in wt % of thefree alkylene glycol produced in less than about one or more of: 2, 3,4, 5, 6, 7, 8, 9, 10, 12, and 15. Method 100 may include an amount in wt% of the free alkylene glycol produced in less than about one or moreof: 5, 10, 15, 20, 25, 30, 35, and 40. Method 100 may include an amountin wt % of the free alkylene glycol produced between any of thepreceding values, for example, between about 4 and about 6, or betweenabout 3 and about 5. Method 100 may include an amount in wt % of thefree alkylene glycol in less than about 2 wt %.

In various embodiments, an alkoxylated bio-oil composition is provided.The alkoxylated bio-oil composition may include an alkoxylated bio-oil.The alkoxylated bio-oil may be derived from a dewatered bio-oil. Thealkoxylated bio-oil composition may include a free alkylene glycol inless than about 40 wt % compared to an amount of the alkoxylatedbio-oil. The amount of the free alkylene glycol may be present in thealkoxylated bio-oil composition in an amount in wt % of less than aboutone or more of: 40, 35, 30, 25, 20, 15, 10, and 5, e.g., less than about40 wt %. The amount of the free alkylene glycol may be present in thealkoxylated bio-oil composition in an amount in wt % between any two ofthe preceding values, for example between about 10 and about 15, orbetween about 10 and about 30. For example, the amount of the freealkylene glycol may be present in the alkoxylated bio-oil composition inless than about 5 wt %. The free alkylene glycol may include mono andpoly alkylene glycols. The free alkylene glycol may occur, for example,according to reaction of the alkoxylation reagent with water, withitself, side reactions, and the like.

The alkoxylated bio-oil may include polyalkylene glycol units covalentlybound to one or more of: an acid, an alcohol, and a phenol grouporiginated in the dewatered bio-oil. The polyalkylene glycol units mayform one or more of: an ester, an ether, and a phenolic ether with thedewatered bio-oil.

The alkoxylated bio-oil composition may include an alkoxylated bio-oilderived from a bio-oil. The bio-oil may be produced by pyrolysis of abiomass. The bio-oil may be produced by catalytic pyrolysis of abiomass. The biomass may originate from wood or otherlignocellulosic-containing biomass.

The alkoxylated bio-oil composition may include an alkoxylated bio-oil.The alkoxylated bio-oil may be derived from a dewatered bio-oil. Thedewatered bio-oil may include water in less than about 3 wt % comparedto the amount of the dewatered bio-oil. The dewatered bio-oil mayinclude water in a wt % of less than about one or more of: 30, 25, 20,15, 10, 5, 4, 3, 2, and 1. The dewatered bio-oil may include water in awt % between any of the preceding values, for example, between about 4and about 10, or between about 3 and about 5.

The dewatered bio-oil used to produce the alkoxylated bio-oil mayinclude water in less than about 3 wt % compared to an amount ofdewatered bio-oil. The presence of water in an alkoxylation reactionwith bio-oil and an alkoxylating reagent may produce a free alkyleneglycol, such as propylene glycol, upon reaction of the water with thealkoxylating reagent, such as propylene oxide. Increasing amounts of thefree alkylene glycol may result in an alkoxylated bio-oil compositionthat is unsuitable for preparing materials, such as polyurethane foams.The alkoxylation of a dewatered bio-oil including water in about 1 wt %may produce a free alkylene glycol in about 3.2 wt %.

The alkoxylated bio-oil may result from a direct alkoxylation of adewatered bio-oil with an alkoxylation reagent. The term “directalkoxylation” means alkoxylation of a bio-oil that has not undergoneother functionalization reactions after pyrolysis and prior to thedirect alkoxylation. Competitive reactions may occur during the directalkoxylation process, e.g., dehydration, as described herein. A reactionis to the breaking or making of chemical bonds in the compounds withinthe bio-oil.

The alkoxylation reagent may include an epoxide, commonly known as anoxirane or an alkylene oxide. The alkoxylation reagent may includeethylene oxide. The alkoxylation reagent may include ethylene oxidesubstituted with a linear or branched C₁-C₆ alkyl, such as propyleneoxide. The alkoxylation reagent may include ethylene oxide substitutedwith a C₃-C₆ cycloalkyl group, such as 2-cyclohexyloxirane or7-oxabicyclo[4.1.0]heptane. The alkoxylation reagent may includeethylene oxide substituted with a C₄-C₁₀ aryl or heteroaryl group, suchas 2-phenyloxirane. The alkoxylation reagent may include one or more ofa linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.

The alkoxylation reagent may include a cyclic carbonate. The cycliccarbonate may include ethylene carbonate. The cyclic carbonate mayinclude trimethylene carbonate. The cyclic carbonate may be substitutedwith a linear or branched C₁-C₆ alkyl, such as propylene carbonate. Thecyclic carbonate may be substituted with a C₃-C₆ cycloalkyl group. Thecyclic carbonate may be substituted with a C₄-C₁₀ aryl or heteroarylgroup. The cyclic carbonate may include one or more of a linear orbranched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀ aryl orheteroaryl group.

The alkoxylation reagent may include one or more of an epoxide and acyclic carbonate.

The alkoxylated bio-oil composition may be prepared by providing adewatered bio-oil. The alkoxylated bio-oil composition may be preparedby contacting the dewatered bio-oil with an alkoxylation reagent. Thealkoxylated bio-oil composition may be prepared by contacting thedewatered bio-oil with an alkoxylation reagent in the presence of apromoter, such as an alkali metal hydroxide, and the like. Thealkoxylated bio-oil composition may be prepared under reactionconditions effective to form the alkoxylated bio-oil composition.

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by one or more of: a reduced viscosity, anincreased molecular weight, a lower gel permeation chromatographyretention time, a lowered acid value, and a reduced percentage of freehydroxyl groups with respect to molecular weight (hydroxyl value).

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by a reduced viscosity. The reduced viscosity maybe greater than about 1%. The reduced viscosity may be less than aboutone or more of: 100%, 99%, 98%, 97%, 96%, 95%, 94%, 93%, 92%, 91%, 90%,85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%,15%, 10%, and 5%. The reduced viscosity of the alkoxylated bio-oil incomparison to a dewatered bio-oil may be a value between any of thepreceding values, for example, between about 85% and about 90%, orbetween about 50% and about 80%.

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by an increased molecular weight. The increasedmolecular weight may be at least about one or more of: 101%, 102%, 103%,104%, 105%, 106%, 107%, 108%, 109%, 110%, 115%, 120%, 125%, 130%, 135%,140%, 145%, 150%, 155%, 160%, 165%, 170%, 175%, 180%, 185%, 190%, 195%,and 200%. The increased molecular weight of the alkoxylated bio-oil incomparison to a dewatered bio-oil may be between any of the precedingvalues, for example, between about 101% and about 105%, or between about135% and about 170%. The increased molecular weight of the alkoxylatedbio-oil in comparison to a dewatered bio-oil may be greater than 200%.

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by a lower gel permeation chromatographyretention time. Since alkoxylation of dewatered bio-oil may produce analkoxylated bio-oil with increased molecular weight, and thus increasedsize, the percentage of time spent in the stationary phase of gelpermeation chromatography may decrease. The percentage of time analkoxylated bio-oil spends in the stationary phase of gel permeationchromatography may decrease relative to a dewatered bio-oil in minutesby at least about one or more of: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14,16, 18, 20, 22, 24, 26, 28, and 30. The percentage of time analkoxylated bio-oil spends in the stationary phase during gel permeationchromatography may decrease relative to a dewatered bio-oil in minutesbetween any of the preceding values, for example, between about 1 andabout 5, or between about 2 and about 10. The percentage of time analkoxylated bio-oil spends in the stationary phase during gel permeationchromatography may decrease relative to a dewatered bio-oil by an amountgreater than 30 min. The retention times may vary along with variationsin flow rate and choice of stationary phase material, for example.

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by a reduced percentage of free hydroxyl groupswith respect to molecular weight, i.e., a reduced number of freehydroxyls in a compound per the molecular weight of the compound. Thealkoxylated bio-oil composition may be characterized in comparison to adewatered bio-oil by a reduced hydroxyl value. In other words, aconstant number of free hydroxyls and an increasing molecular weightwill reduce the percentage of free hydroxyl groups with respect tomolecular weight. Alternatively, a reduction in the number of hydroxylgroups and a constant or increasing molecular weight will reduce thepercentage of free hydroxyl groups with respect to molecular weight. Thepercentage of free hydroxyl groups with respect to molecular weight maybe reduced by at least about one or more of: 1%, 2%, 3%, 4%. 5%. 6%, 7%,8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%,75%, 80%, 85%, 90%, 95%, and 99%. The percentage of free hydroxyl groupswith respect to molecular weight may be reduced between any of thepreceding values, for example, between about 5% and about 10%, orbetween about 35% and about 50%.

The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by a reduced percentage of free carboxylic acidswith respect to molecular weight, i.e., a reduced number of freecarboxylic acids in a compound per the molecular weight of the compound.The alkoxylated bio-oil composition may be characterized in comparisonto a dewatered bio-oil by a reduced acid value. In other words, aconstant number of free carboxylic acids and an increasing molecularweight will reduce the percentage of free carboxylic acids with respectto molecular weight. The percentage of free carboxylic acids withrespect to molecular weight may be reduced by at least about one or moreof: 1%, 2%, 3%, 4%. 5%. 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%,40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and 99%. Thepercentage of free carboxylic acids with respect to molecular weight maybe reduced between any of the preceding values, for example, betweenabout 5% and about 10%, or between about 35% and about 50%.

FIG. 2 is a flow diagram illustrating an example method 200 forpreparing a copolymer composition. In various embodiments, method 200may include providing a polymerization precursor mixture. Thepolymerization precursor mixture may include a crosslinking reagent. Thecrosslinking reagent may be configured to form a copolymer incombination with an alkoxylated bio-oil. The alkoxylated bio-oilcomposition may include an alkoxylated bio-oil. The method may include204 reacting an alkoxylated bio-oil composition with the polymerizationprecursor mixture. The alkoxylated bio-oil composition may include thealkoxylated bio-oil. The method may include reaction conditionseffective to form the copolymer composition.

Method 200 may include an alkoxylated bio-oil composition including analkoxylated bio-oil derived from a dewatered bio-oil. The dewateredbio-oil may include water in less than about 3 wt % compared to anamount of dewatered bio-oil. The dewatered bio-oil may include water inwt % compared to an amount of dewatered bio-oil in less than about oneor more of: 30, 25, 20, 15, 10, 5, 4, 3, 2, and 1. The dewatered bio-oilmay include water in a wt % in comparison to an amount of dewateredbio-oil between any of the preceding values, for example, between about2 and about 3, or between about 5 and about 10.

The alkoxylated bio-oil composition may include an alkoxylated bio-oilderived from a bio-oil. The bio-oil may be produced by pyrolysis of abiomass. The bio-oil may be produced by catalytic pyrolysis of abiomass. The biomass may originate from wood or otherlignocellulosic-containing biomass. The alkoxylated bio-oil may resultfrom a direct alkoxylation of a dewatered bio-oil with an alkoxylationreagent.

The alkoxylation reagent may include an epoxide, commonly known as anoxirane or an alkylene oxide. The alkoxylation reagent may includeethylene oxide. The alkoxylation reagent may include ethylene oxidesubstituted with a linear or branched C₁-C₆ alkyl, such as propyleneoxide. The alkoxylation reagent may include ethylene oxide substitutedwith a C₃-C₆ cycloalkyl group, such as 2-cyclohexyloxirane or7-oxabicyclo[4.1.0]heptane. The alkoxylation reagent may includeethylene oxide substituted with a C₄-C₁₀ aryl or heteroaryl group, suchas 2-phenyloxirane. The alkoxylation reagent may include one or more ofa linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.

The alkoxylation reagent may include a cyclic carbonate. The cycliccarbonate may include ethylene carbonate. The cyclic carbonate mayinclude trimethylene carbonate. The cyclic carbonate may be substitutedwith a linear or branched C₁-C₆ alkyl, such as propylene carbonate. Thecyclic carbonate may be substituted with a C₃-C₆ cycloalkyl group. Thecyclic carbonate may be substituted with a C₄-C₁₀ aryl or heteroarylgroup. The cyclic carbonate may include one or more of a linear orbranched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀ aryl orheteroaryl group.

The alkoxylation reagent may include one or more of an epoxide and acyclic carbonate.

Method 200 may include a polymerization precursor mixture. Thepolymerization precursor mixture may include a crosslinking reagent. Thecrosslinking reagent may include at least two isocyanate groups, such asa polyisocyanate reagent. The reagent may be effective to form thecopolymer composition upon reaction with the alkoxylated bio-oilcomposition. The polymerization precursor mixture may include one ormore of: toluene diisocyanate, methylene diphenyl diisocyanate, 1,6hexamethylene diisocyanate,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, and4,′4-diisocyanato dicyclohexylmethane. The polymerization precursormixture may include one or more of: ethylene diisocyanate,1,4-tetramethylene diisocyanate, 1,12-dodecane diisocyanate,1,3-cyclobutane diisocyanate, 1,3-cyclohexane diisocyanate,1,4-cyclohexane diisocyanate, hexahydrotolylene-2,4-diisocyanate,hexahydrotolylene-2,6-diisocyanate, diphenylmethane 2,4′-diisocyanate,diphenylmethane 4-4′-diisocyanate, naphthylene-1,5-diisocyanate,triphenyl methane-4,4′,4″-triisocyanate, polyphenyl-polymethylenepolyisocyanate, m-isocyanatophenyl sulphonyl isocyanate,p-isocyanatophenyl sulphonyl isocyanate, perchlorinated arylpolyisocyanate, polyisocyanate containing carbodiimide groups,polyisocyanates containing allophanate groups, polyisocyanatescontaining isocyanurate groups, polyisocyanates containing urethanegroups, polyisocyanate containing acrylated urea groups, polyisocyanatesprepared by telmerization reactions, polyisocyanates containing estergroups, polyisocyanates containing polymer fatty acid groups, and thelike.

Method 200 for producing the copolymer composition may include acopolymer including a polyurethane. The polyurethane may be produced bycontacting a polymerization precursor mixture including a polyisocyanatereagent to the alkoxylated bio-oil composition.

The polymerization precursor mixture may include a blowing agent. Theblowing agent may include water. The blowing agent may include ahydrocarbon. The blowing agent may include a halogenated hydrocarbon.The blowing agent may include a volatile organic compound.

The polymerization precursor mixture may include a surfactant. Thesurfactant may be a surfactant configured to support polyurethane foamformation. The surfactant may include, for example, a siliconesurfactants. Suitable silicone surfactants are commercially available,for example, the DABCO® series of silicone surfactants (Air Products andChemicals, Inc., Allentown, Pa.), including, for example, one or moreof: SI3102, DC198, DC193, DC2525, DC2584, DC2585, DC3042, DC3043,DC5000, DC5043, and the like, e.g., DABCO® DC193.

Method 200 for producing the copolymer composition may includecontacting a viscosity-reducing modifier to the alkoxylated bio-oiland/or the polymerization precursor mixture. The method may includecontacting the viscosity-reducing modifier to the alkoxylated bio-oilpolyol. The method may include contacting the viscosity-reducingmodifier to the polymerization precursor mixture. The viscosity-reducingmodifier may be a viscosity-reducing modifier polyol. Theviscosity-reducing modifier polyol may include a petroleum-derivedpolyol, a polyester polyol, a bio-based polyester polyol, and the like.Suitable bio-based polyester polyols may include, but may be not limitedto, bio-based polyester polyols, such as Priplast bio-based polyesterpolyols (Croda USA, New Castle, Del.). The viscosity-reducing modifierpolyol may include a diol, a glycol, a triol, a tetraol, and the like.The viscosity-reducing modifier polyol may include one or more of:ethylene glycol, propylene glycol, neopentyl glycol,2-methyl-1,3-propane diol, glycerol, trimethylolpropane, hexanetriol,butanetriol, trimethylolethane, pentaerythritol, mannitol, sorbitol,methylglucoside, diethylene glycol, polybutylene glycol, and the like.

The polymerization precursor mixture may include a polyol. The polyolmay include a petroleum-derived polyol. The polyol may include apolyester polyol. The polyol may include a bio-based polyester polyol.Suitable bio-based polyester polyols may include, but may be not limitedto, bio-based polyester polyols, such as Priplast bio-based polyesterpolyols (Croda USA, New Castle, Del.). The polyol may include a diol, aglycol, a triol, a tetraol, and the like. The polyol may include one ormore of: ethylene glycol, propylene glycol, neopentyl glycol,2-methyl-1,3-propane diol, glycerol, trimethylolpropane, hexanetriol,butanetriol, trimethylolethane, pentaerythritol, mannitol, sorbitol,methylglucoside, diethylene glycol, polybutylene glycol, and the like.

The polyol may be present in a weight % between about 5 and about 95compared to an amount of the alkoxylated bio-oil. The polyol may bepresent in a weight % of at least about one or more of: 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100. Thepolyol may be present in a weight % between any of the preceding values,for example, between about 20 and about 45, or between about 30 andabout 35. One or more of the petroleum polyol and the bio-basedpolyester polyol may be incorporated into the copolymer as a polyolmonomer unit. One or more of the petroleum polyol and the bio-basedpolyester polyol may serve as a viscosity-reducing agent. One or more ofthe petroleum polyol and the bio-based polyester polyol may form acopolymer with the crosslinking reagent.

The polymerization precursor mixture may include an alkanol amine. Thealkanol amine may condense with unreacted carboxylic acids in thealkoxylated bio-oil composition. The reaction of alkanol amine andcarboxylic acids may produce hydroxyamides. Hydroxyamides may facilitatepolyurethane formation by increasing the reactivity of the hydroxyamidealcohols through inductive effects.

The polymerization precursor mixture may include a promoter. Thepromoter may include a polyurethane promoter. A polyurethane promotermay include a base. The base may include a non-nucleophilic base. Thebase may serve as a proton transfer agent. The base may include atrialkylamine. The base may include triethylene amine, pyridine,dimethylamino pyridine, and the like. The polyurethane promoter mayinclude an acid. The acid may include a Brønsted acid or a Lewis acid.Suitable polyurethane promoters (catalysts) may include, but are notlimited to, amine compounds, hypophosphite salts, zeolites, metalcomplexes such as stannous or stannic salts, and combinations thereof.Suitable amine catalysts may include, but are not limited to, tertiaryamines such as triethylenediamine, dimethylcyclohexylamine,dimethylethanolamine, and the like. Hypophosphite salts include, forexample, alkali metal salts such as sodium hypophosphite and alkaliearth metal salts such as calcium hypophosphite, and the like. Catalystsfor polyurethane polymerization may be based on metallic compounds ofmercury, lead, tin, bismuth, zinc, and the like. Such metallic compoundsmay include one or more different oxidation states (I), (II), (III), or(IV), for example, tin(II) and tin(IV) compounds. Such metalliccompounds of mercury, lead, tin, bismuth, zinc, and the like, mayinclude metallic carboxylates, oxides, mercaptides, and the like. Forexample, mercury carboxylates, bismuth carboxylates, zinc carboxylates,tin carboxylates and the like may be suitable catalysts. For example,metal carboxylate compounds may include one or more carboxylates. Suchone or more carboxylates may include monocarboxylates, or two or morecarboxylates in the same organic carboxylate, such as the dicarboxylateoxalate in tin (II) oxalate. Metal carboxylate compounds may alsoinclude alkyl carboxylates with one or more pendant alkyl groups, e.g.,dialkyl tin dicarboxylates such as dibutyltin dilaurate. For example,the method may include providing a tin (II) oxalate as a catalyst.

The polymerization precursor mixture may include an amine. The amine mayinclude a tertiary amine. The amine may include a trialkylamine. Forexample, the amine may include one or more of: DABCO® BDMA, DABCO®MP601, DABCO® RP202, DABCO® 1027, DABCO® 1028, DABCO® 2033, DABCO® 2039,DABCO® 2040, DABCO® 33-LV, DABCO® 33-LX, DABCO® 8154, DABCO® B-16, andthe like (Air Products and Chemicals, Inc., Allentown, Pa.). The aminemay include a polylalkylamino alkyl ether, for example, DABCO® BL-19(Air Products and Chemicals, Inc., Allentown, Pa.).

The polymerization precursor mixture may include one or more of: apetroleum polyol, a bio-based polyester polyol, water, a silicone foamforming surfactant, a trialkylamine, a polyalkylamino alkyl ether, analkanol amine, a promoter, an antioxidant, a flame retardant, anultraviolet light stabilizer, a pigment, a dye, a plasticizer, and thelike.

Method 200 may include a polymerization precursor mixture. Thepolymerization precursor mixture may include a crosslinking reagentincluding at least two carboxylic acid derivative groups, such as apolycarboxylic acid derivative reagent. The carboxylic acid derivativesmay include one or more of: a carboxylic acid, an acyl halide, an ester,and an anhydride. The polymerization precursor mixture may include areagent including at least one cyclic anhydride. The reagent may beeffective to form the copolymer composition upon reaction with thealkoxylated bio-oil composition. The polymerization precursor mixturemay include a reagent including one or more of: oxalic acid, malonicacid, maleic acid, succinic acid, fumaric acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid brassilicacid, dodecanedioic acid, hexadecanedioic acid, 1,2-phthatlic acid,1,3-phthatlic acid, 1,4-phthatlic acid, trimellitic acid; C₁-C₆ estersof any of the preceding; corresponding acyl chlorides of any of thepreceding, such as oxalyl chloride; C₁-C₇ anhydrides of any of thepreceding; succinic anhydride, maleic anhydride, phthalic anhydride,pyromellitic dianhydride, 1,2-cyclopentanedicarboxylic anhydride,glutaric anhydride, 2,7-oxepanedione, naphthalenetetracarboxylicdianhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acidanhydride, and the like.

Method 200 may include reaction conditions in the presence of apromoter. For example, the catalyst may be a polyester polymerizationcatalyst for reacting the alkoxylated bio-oil composition with apolymerization precursor mixture including a polycarboxylic acidderivative reagent, as described herein, to form the copolymercomposition. Suitable polyester catalysts may include, but are notlimited to, Brønsted acids, Brønsted bases, and Lewis acids. Forexample, suitable Brønsted acids may include inorganic acids, such ashydrochloric acid, hydroiodic acid, sulfuric acid, and the like. Forexample, suitable Brønsted acids may include organic acids, such asacetic acid, propionic acid, para-toluene sulfonic acid, triflic acid,protonated amines, and the like. For example, suitable Brønsted basesmay include alkali metal hydroxides, such as sodium hydroxide orpotassium hydroxide; alkali metal carbonates and bicarbonates, such assodium carbonate, cesium carbonate, and sodium bicarbonate; amines, suchas triethylamine, pyridine, dimethylamino pyridine, and the like. Forexample, suitable Lewis acids may include reagents based on transitionmetals, post-transition metals, metalloids, and lanthanides, forexample, reagents including scandium, titanium, iron, tin, zinc, copper,gold, aluminum, tin, bismuth, boron, silicon, lanthanium, samarium, andeuropium. For example, Lewis acids may include scandium triflate, irontrichloride, zinc chloride, copper chloride, aluminum trichloride,aluminum oxide, boron trichloride, boron trifluoride, and the like.

Method 200 for preparing the copolymer composition may include acopolymer including a polyester. The polyester may be produced by areaction between a polymerization precursor mixture including acrosslinking reagent including a polycarboxylic acid derivative reagentand the alkoxylated bio-oil composition.

Method 200 may include a polymerization precursor mixture. Thepolymerization precursor mixture may include a crosslinking reagent. Thecrosslinking reagent may include a phenol-containing compound. Thephenol compound may be substituted at an aryl carbon with at least one1-hydroxyalkyl group, e.g., hydroxymethyl group to form a benzylicalcohol. The 1-hydroxyalkyl group may be represented by —CR¹R²OH,wherein R¹ and R² may be H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅,CHO, CHO, CH₂CHO, CH₂CH₂CHO, CH₂CH₂CH₂CHO, C(O)CH₃, or CH₂C(O)CH₃.

The crosslinking reagent may be effective to form the copolymercomposition upon reaction with the alkoxylated bio-oil composition. Thecrosslinking reagent may include, for example, one or more of:2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol,4-(hydroxymethyl)-2-methylphenol, (2-hydroxy-1,3-phenylene)dimethanol,2,6-bis(hydroxylmethyl)-p-cresol,5-(t-butyl)-2-hydroxy-1,3-phenylene)dimethanol,4-hydroxy-1,3-phenylene)dimethanol, and the like.

Alternatively, or in addition to, the polymerization precursor mixturemay include a crosslinking reagent including a phenol compound and the1-hydroxyalkyl moiety may be installed on the phenol compound in situ.The polymerization precursor mixture may further include an aldehyde.The polymerization precursor mixture may include, for example,formaldehyde. The polymerization precursor mixture may include one ormore of: formaldehyde, acetaldehyde, proprionaldehyde, butryaldehyde,glyoxal, propane-1,3-dial, butane-1,4-dial, glutaraldehyde, and thelike.

The polymerization precursor mixture may include a ketone. Thepolymerization precursor mixture may include one or more of: acetone,2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione,pentane-2,4-dione, and the like. The polymerization precursor mixturemay include an aldehyde and a ketone, such as formaldehyde and acetone.One or more of the aldehyde and ketone may be at least partly soluble inwater.

The polymerization precursor mixture may include one or more of analdehyde and a ketone.

The amount of aldehyde and/or ketone may be present in thepolymerization precursor mixture in an amount less than an amount of thephenol compound present in the polymerization precursor mixture. Theamount of aldehyde and/or ketone may be present in the polymerizationprecursor mixture in amount substantially equal to an amount of thephenol compound present in the polymerization precursor mixture. Theamount of aldehyde and/or ketone may be present in the polymerizationprecursor mixture in amount greater than an amount of the phenoliccompound present in the polymerization precursor mixture.

The polymerization precursor mixture may include a phenol-formaldehyderesin and one or more of an aldehyde and ketone. The polymerizationprecursor mixture may include a phenol-formaldehyde resin and noaldehyde or ketone in order to prepare a copolymer blend. Thepolymerization precursor mixture may include a bio-oil, the bio-oilincluding a phenol moiety. The polymerization precursor including thebio-oil including the phenol moiety may further include one or more ofan aldehyde and ketone.

Method 200 for preparing the copolymer composition may include acopolymer including a phenol-formaldehyde resin. The phenol-formaldehyderesin may be produced by a reaction between a polymerization precursormixture including a crosslinking reagent including a phenol compoundsubstituted at an aryl carbon with a 1-hydroxyalkyl group and thealkoxylated bio-oil composition.

Method 200 may include a polymerization precursor mixture. Thepolymerization precursor mixture may include a phenol compound, a ureaor a substituted urea, and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal,benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone,2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione. Thesubstituted urea may include alkyl N—N′-substitution, for example, withmethyl groups.

The polymerization precursor mixture may include aphenol-urea-formaldehyde resin, a urea or substituted urea, and one ormore of an aldehyde and ketone. The polymerization precursor mixture mayinclude a phenol-urea-formaldehyde resin and no urea or substituted ureaand no aldehyde or ketone in order to prepare a copolymer blend. Thepolymerization precursor mixture may include a bio-oil, the bio-oilincluding a phenol moiety. The polymerization precursor including thebio-oil including the phenol moiety may further include a urea orsubstituted urea and one or more of an aldehyde and ketone.

Method 200 for preparing the copolymer composition may include acopolymer including a phenol-urea-formaldehyde resin. Thephenol-urea-formaldehyde resin may be produced by a reaction between apolymerization precursor mixture including a crosslinking reagentincluding a phenol compound substituted at an aryl carbon with abenzylic urea group, wherein the benzylic urea group is N-substitutedwith a —CR¹R²OH group, e.g., —CH₂OH, and the alkoxylated bio-oilcomposition.

Method 200 may include a polymerization precursor mixture. Thepolymerization precursor mixture may a urea or a substituted urea, andone or more of: formaldehyde, acetaldehyde, propionaldehyde,butryaldehyde, valeraldehyde, glutaraldehyde glyoxal, benzaldehyde,propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone, 2-pentanone,3-pentanone, butane-2,3-dione, and pentane-2,4-dione. The substitutedurea may include alkyl N—N′-substitution, for example, with methylgroups.

The polymerization precursor mixture may include a urea-formaldehyderesin, a urea or substituted urea, and one or more of an aldehyde andketone. The polymerization precursor mixture may include aurea-formaldehyde resin and no urea or substituted urea and no aldehydeor ketone in order to prepare a copolymer blend.

Method 200 for preparing the copolymer composition may include acopolymer including a urea-formaldehyde resin. The urea-formaldehyderesin may be produced by a reaction between a polymerization precursormixture including a crosslinking reagent including a urea groupN—N′-substituted with a —CR¹R²OH group, e.g., CH₂OH, and the alkoxylatedbio-oil composition.

It is not intended that the components of the polymerization precursormixture be premixed or allowed to stand prior to the addition of thealkoxylated bio-oil composition. The components of the polymerizationprecursor mixture may be added in a step-wise fashion in order toprevent premature reaction and production of unwanted side products. Forexample, a promoter may be added to the alkoxylated bio-oil prior to theaddition of the crosslinking reagent. For example, a petroleum polyolmay be added to the alkoxylated bio-oil prior to the addition of thecrosslinking reagent.

Method 200 may include a reaction conditions effective to form thecopolymer composition. The reaction conditions may include a reactiontemperature in ° C. of at least about one or more of: 0, 10, 20, 25, 30,35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120,125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, and 180. Thereaction conditions may include a reaction temperature in ° C. betweenany of the preceding values, for example, between about 60 and about100, or between bout 30 and about 180.

The reaction conditions may include a reaction pressure in pounds persquare inch of at least about one or more of: 0, 15, 25, 50, 75, 100,125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450,475, 500, 525, 550, 575, and 600. The reaction conditions may include areaction pressure in pounds per square inch between any of the precedingvalues, for example, between about 15 and about 200, or between about100 and about 500.

Method 200 may further include configuring the copolymer composition asone or more of: a foam, a spray foam, an extrusion, an injectionmolding, a coating, an adhesive, an elastomer, a foundry resin, asealant, a casting, a fiber, a potting compound, a reaction injectionmolded (RIM) plastic, a microcellular elastomer or foam, and an integralskin foam.

In various embodiments, a copolymer composition is provided. Thecopolymer composition may include a copolymer. The copolymer may includean alkoxylated bio-oil unit. The alkoxylated bio-oil unit may be derivedfrom an alkoxylated bio-oil composition including an alkoxylatedbio-oil. The copolymer may include a cross-linking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking unit may be effective to crosslink more than onealkoxylated bio-oil unit to form the copolymer.

The copolymer composition may include an amount of one or more of: afree alkylene glycol and a cross-linked polyalkylene glycol in less thanabout 10 wt % compared to an amount of the copolymer. The copolymercomposition may include an amount in wt % of one or more of the freealkylene glycol and the cross-linked polyalkylene glycol of less thanabout one or more of: 40, 35, 30, 25, 20, 15, 10 and 5. The copolymercomposition may include an amount in wt % of one or more of the freealkylene glycol and the cross-linked polyalkylene glycol between any ofthe preceding values, for example, between about 5 and about 10, orbetween about 10 and about 15.

The copolymer may include an alkoxylated bio-oil unit derived from analkoxylated bio-oil derived from a dewatered bio-oil. The dewateredbio-oil may include water in less than about 3 wt % compared to theamount of the dewatered bio-oil. The dewatered bio-oil may include waterin a wt % of less than about one or more of: 30, 25, 20, 15, 10, 5, 4,3, 2, and 1. The dewatered bio-oil may include water in a wt % betweenany of the preceding values, for example, between about 4 and about 10,or between about 3 and about 5.

The dewatered bio-oil used to produce the alkoxylated bio-oil mayinclude water in less than about 3 wt % compared to an amount ofdewatered bio-oil. The presence of water in an alkoxylation reactionwith bio-oil and an alkoxylating reagent may produce a free alkyleneglycol, such as propylene glycol, upon reaction of the water with thealkoxylating reagent, such as propylene oxide. Increasing amounts of thefree alkylene glycol may result in an alkoxylated bio-oil compositionthat is unsuitable for preparing materials, such as polyurethane foams.The alkoxylation of a dewatered bio-oil including water in about 1 wt %may produce a free alkylene glycol in about 3.2 wt %. The alkoxylationof the dewatered bio-oil may produce an alkoxylated bio-oil. Thealkoxylated bio-oil may provide the alkoxylated bio-oil units in thecopolymer.

The alkoxylated bio-oil may be derived from a dewatered bio-oil derivedfrom a bio-oil. The bio-oil may be produced from pyrolysis of a biomass.The bio-oil may be produced from catalytic pyrolysis of a biomass. Thebiomass may originate from wood or other lignocellulosic-containingbiomass. The alkoxylated bio-oil may result from a direct alkoxylationof a dewatered bio-oil with an alkoxylation reagent.

The alkoxylation reagent may include an epoxide, commonly known as anoxirane or an alkylene oxide. The alkoxylation reagent may includeethylene oxide. The alkoxylation reagent may include ethylene oxidesubstituted with a linear or branched C₁-C₆ alkyl, such as propyleneoxide. The alkoxylation reagent may include ethylene oxide substitutedwith a C₃-C₆ cycloalkyl group, such as 2-cyclohexyloxirane or7-oxabicyclo[4.1.0]heptane. The alkoxylation reagent may includeethylene oxide substituted with a C₄-C₁₀ aryl or heteroaryl group, suchas 2-phenyloxirane. The alkoxylation reagent may include one or more ofa linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.

The alkoxylation reagent may include a cyclic carbonate. The cycliccarbonate may include ethylene carbonate. The cyclic carbonate mayinclude trimethylene carbonate. The cyclic carbonate may be substitutedwith a linear or branched C₁-C₆ alkyl, such as propylene carbonate. Thecyclic carbonate may be substituted with a C₃-C₆ cycloalkyl group. Thecyclic carbonate may be substituted with a C₄-C₁₀ aryl or heteroarylgroup. The cyclic carbonate may include one or more of a linear orbranched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀ aryl orheteroaryl group.

The alkoxylation reagent may include one or more of an epoxide and acyclic carbonate. The nature of the alkoxylation reagent with determinethe nature of the alkoxylated bio-oil used to prepare the copolymercomposition. The nature of the alkoxylated bio-oil may influence theproperties of the copolymer composition.

The alkoxylated bio-oil composition may be prepared by providing adewatered bio-oil. The alkoxylated bio-oil composition may be preparedby contacting the dewatered bio-oil with an alkoxylation reagent. Thealkoxylated bio-oil composition may be prepared by contacting thedewatered bio-oil with an alkoxylation reagent in the present of apromoter, such as an alkali metal hydroxide, and the like. Thealkoxylated bio-oil composition may be prepared under reactionconditions effective to form the alkoxylated bio-oil composition.

The copolymer composition may include a crosslinking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking reagent may include at least two isocyanate groups. Thecrosslinking reagent may be effective to form the copolymer compositionupon reaction with the alkoxylated bio-oil composition. The crosslinkingreagent may include one or more of: toluene diisocyanate, methylenediphenyl diisocyanate, 1,6 hexamethylene diisocyanate,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, and4,′4-diisocyanato dicyclohexylmethane. The polymerization precursormixture may include one or more of: ethylene diisocyanate,1,4-tetramethylene diisocyanate, 1,12-dodecane diisocyanate,1,3-cyclobutane diisocyanate, 1,3-cyclohexane diisocyanate,1,4-cyclohexane diisocyanate, hexahydrotolylene-2,4-diisocyanate,hexahydrotolylene-2,6-diisocyanate, diphenylmethane 2,4′-diisocyanate,diphenylmethane 4-4′-diisocyanate, naphthylene-1,5-diisocyanate,triphenyl methane-4,4′,4″-triisocyanate, polyphenyl-polymethylenepolyisocyanate, m-isocyanatophenyl sulphonyl isocyanate,p-isocyanatophenyl sulphonyl isocyanate, perchlorinated arylpolyisocyanate, polyisocyanate containing carbodiimide groups,polyisocyanates containing allophanate groups, polyisocyanatescontaining isocyanurate groups, polyisocyanates containing urethanegroups, polyisocyanate containing acrylated urea groups, polyisocyanatesprepared by telmerization reactions, polyisocyanates containing estergroups, polyisocyanates containing polymer fatty acid groups, and thelike.

The copolymer composition may include a copolymer. The copolymer mayinclude a polyurethane. The polyurethane may include alkoxylated bio-oilunits and urethane (carbamate) crosslinking units. The polyurethane mayresult from contacting an alkoxylated bio-oil composition with apolyisocyanate crosslinking reagent. The polyurethane may be referred toas a polyether polyurethane, a polyurethane polyether, and the like.

The copolymer composition may include a crosslinking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking reagent may include at least two carboxylic acid derivativegroups. The carboxylic acid derivatives may include one or more of: acarboxylic acid, an acyl halide, an ester, and an anhydride. Thepolymerization precursor mixture may include a reagent including atleast one cyclic anhydride. The reagent may be effective to form thecopolymer composition upon reaction with the alkoxylated bio-oilcomposition. The crosslinking reagent may include a reagent includingone or more of: oxalic acid, malonic acid, maleic acid, succinic acid,fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid brassilic acid, dodecanedioic acid,hexadecanedioic acid, 1,2-phthatlic acid, 1,3-phthatlic acid,1,4-phthatlic acid, trimellitic acid; C₁-C₆ esters of any of thepreceding; corresponding acyl chlorides of any of the preceding, such asoxalyl chloride; C₁-C₇ anhydrides of any of the preceding; succinicanhydride, maleic anhydride, phthalic anhydride, pyromelliticdianhydride, 1,2-cyclopentanedicarboxylic anhydride, glutaric anhydride,2,7-oxepanedione, naphthalenetetracarboxylic dianhydride,tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, andthe like.

The copolymer composition may include a copolymer. The copolymer mayinclude a polyester. The polyester may include alkoxylated bio-oil unitsand ester crosslinking units. The polyester may result from contactingan alkoxylated bio-oil composition with a polycarboxylic acid derivatecrosslinking reagent. The polyester may be referred to as a polyesterether, a polyester polyether, a polyether ester, and the like.

The copolymer composition may include a crosslinking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking reagent may include a phenol compound substituted at anaryl carbon with a 1-hydroxyalkyl group. The crosslinking reagent mayresult from an in situ reaction of a phenol compound and one or more of:formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde,valeraldehyde, benzaldehyde, glyoxal, propane-1,3-dial, butane-1,4-dial,and glutaraldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone,butane-2,3-dione, and pentane-2,4-dione. The phenol compound mayinclude, for example, phenol or a substituted phenol. The phenolcompound may include bio-oil including a phenol moiety.

The copolymer composition may be blended with other polymers andcopolymers, for example, the copolymer composition may be blended with anovolac-type or resol-type resin.

The copolymer composition may include a copolymer. The copolymer mayinclude a phenol-formaldehyde resin. The phenol-formaldehyde resin mayinclude alkoxylated bio-oil units and phenol-methylene crosslinkingunits. The phenol-formaldehyde may result from contacting an alkoxylatedbio-oil composition with a phenol compound substituted with a benzylicalcohol crosslinking reagent. The phenol-formaldehyde resin may bereferred to as a phenol-aldehyde resin, a phenol-ketone resin, and thelike.

The copolymer composition may include a crosslinking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking reagent may result from an in situ reaction of a phenolcompound, a urea or substituted urea, and one or more of: formaldehyde,acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde,benzaldehyde, glyoxal, propane-1,3-dial, butane-1,4-dial, andglutaraldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone,butane-2,3-dione, and pentane-2,4-dione. The phenol compound mayinclude, for example, phenol or a substituted phenol. The phenolcompound may include bio-oil including a phenol moiety.

The copolymer composition may be blended with other polymers andcopolymers, for example, the copolymer composition may be blended with anovolac-type or resol-type resin.

The copolymer composition may include a copolymer. The copolymer mayinclude a phenol-urea-formaldehyde resin. The phenol-urea-formaldehyderesin may include alkoxylated bio-oil units and phenol-methylene-ureacrosslinking units. The phenol-urea-formaldehyde may result fromcontacting an alkoxylated bio-oil composition with a phenol compound inthe presence of a urea or a substituted urea and one or more of analdehyde and a ketone. The phenol-urea-formaldehyde resin may bereferred to as a phenol-urea-aldehyde resin, a phenol-urea-ketone resin,and the like.

The copolymer composition may include a crosslinking unit. Thecrosslinking unit may be derived from a crosslinking reagent. Thecrosslinking reagent may result from an in situ reaction of a urea orsubstituted urea, and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, benzaldehyde, glyoxal,propane-1,3-dial, butane-1,4-dial, and glutaraldehyde, acetone,2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione, andpentane-2,4-dione.

The copolymer composition may be blended with other polymers andcopolymers, for example, the copolymer composition may be blended with anovolac-type or resol-type resin.

The copolymer composition may include a copolymer. The copolymer mayinclude a urea-formaldehyde resin. The urea-formaldehyde resin mayinclude alkoxylated bio-oil units and methylene-urea crosslinking units.The urea-formaldehyde may result from contacting an alkoxylated bio-oilcomposition in the presence of a urea or a substituted urea and one ormore of an aldehyde and a ketone. The urea-formaldehyde resin may bereferred to as a urea-aldehyde resin, a urea-ketone resin, and the like.

The copolymer composition may be configured as one or more of: a foam, aspray foam, an extrusion, an injection molding, a coating, an adhesive,an elastomer, a foundry resin, a sealant, a casting, a fiber, a pottingcompound, a reaction injection molded (RIM) plastic, a microcellularelastomer or foam, and an integral skin foam.

In various embodiments, a method for preparing an alkoxylated bio-oilcomposition is provided. The method may include providing a dewateredbio-oil. The method may include contacting the dewatered bio-oil with analkoxylation reagent under reaction conditions effective to form analkoxylated bio-oil.

The method may include any aspect of the method described herein. Forexample, in some embodiments, the method may include dewatering abio-oil to produce the dewatered by one or more of: distillation, vacuumdistillation, azeotropic distillation, evaporation, salting out, freezedrying, adsorption, desiccation, and centrifugation.

In several embodiments, the alkoxylation reagent may include one or moreof: an epoxide and a cyclic carbonate. The alkoxylation reagent mayinclude one or more of: ethylene oxide optionally substituted with oneor more of a linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group,and a C₄-C₁₀ aryl or heteroaryl group; ethylene carbonate optionallysubstituted with one or more of a linear or branched C₁-C₆ alkyl, aC₃-C₆ cycloalkyl group, and a C₄-C₁₀ aryl or heteroaryl group; andtrimethylene carbonate optionally substituted with one or more of alinear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.

In several embodiments, the reaction conditions may include one or moreof: the alkoxylation reagent being present in an amount greater than 5wt % compared to an amount of the dewatered bio-oil; the presence of apromoter, the promoter including one of an acid and a base; the promoterbeing present in an amount between about 0.005 wt % and 5 wt % comparedto an amount of the dewatered bio-oil; a reaction temperature of betweenabout 80° C. and about 180° C.; a reaction pressure in pounds per squareinch of between about 0 and about 600; the dewatered bio-oil including apyrolytic bio-oil or a catalytic pyrolytic bio-oil; less than about 30wt % water compared to the dewatered bio-oil; and production of a freealkylene glycol byproduct at less than about 40 wt % compared to thedewatered bio-oil.

In various embodiments, the method may include contacting the dewateredbio-oil with a promoter; allowing the dewatered bio-oil and the promotorto react for a period of time prior to contacting the dewatered bio-oilwith the alkoxylation reagent; optionally heating the dewatered bio-oiland the promoter, optionally under reduced pressure, for a period oftime prior to contacting the dewatered bio-oil with the alkoxylationreagent, the promoter may include an alkali metal hydroxide; andoptionally condensing a water vapor into a container separate from thedewatered bio-oil and the promoter prior to contacting the dewateredbio-oil with the alkoxylation reagent.

In various embodiments, an alkoxylated bio-oil composition is provided.The alkoxylated bio-oil composition may include an alkoxylated bio-oil,the alkoxylated bio-oil derived from a dewatered bio-oil; and an amountof a free alkylene glycol of less than about 40 wt % compared to anamount of the alkoxylated bio-oil.

The alkoxylated bio-oil composition may include any aspect of thealkoxylated bio-oil composition described herein. For example, Thealkoxylated bio-oil composition may be characterized by one or more of:including at least one polyalkylene glycol unit covalently bound to oneor more of an acid, an alcohol, and a phenol functionality originated inthe dewatered bio-oil; being produced from a direct alkoxylation of thedewatered bio-oil; the dewatered bio-oil including a pyrolytic bio-oilor a catalytic pyrolytic bio-oil; and in comparison to the dewateredbio-oil, by one or more of: a reduced viscosity, an increased molecularweight, a lower gel permeation chromatography retention time, and areduced hydroxyl value.

In various embodiments, a method for preparing a copolymer compositionis provided. The method may include providing a polymerization precursormixture. The polymerization precursor mixture may include a crosslinkingreagent configured to form a copolymer in combination with analkoxylated bio-oil. The method may include reacting an alkoxylatedbio-oil composition including the alkoxylated bio-oil with thepolymerization precursor mixture under reaction conditions effective toform the copolymer composition.

The method may include any aspect of the method for preparing acopolymer composition described herein. For example, in someembodiments, the alkoxylated bio-oil characterized by one or more of:being produced from a direct alkoxylation of a dewatered bio-oil; thedewatered bio-oil including a pyrolytic bio-oil or a catalytic pyrolyticbio-oil; including at least one polyalkylene glycol unit covalentlybound to one or more of an acid, an alcohol, and a phenol functionalityoriginated in the dewatered bio-oil; and in comparison to the dewateredbio-oil, by one or more of: a reduced viscosity, an increased molecularweight, a lower gel permeation chromatography retention time, and areduced hydroxyl value.

In some embodiments, the crosslinking reagent may include one of: atleast two isocyanate groups; at least two carboxylic acid derivativegroups; one or more of: a carboxylic acid, an ester, a acyl halide, acyclic anhydride, and an anhydride; and a phenol compound substituted atan aryl carbon with at least one —CR¹R²OH, wherein: R¹ is H, CH₃,CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅, CHO, CHO, CH₂CHO, CH₂CH₂CHO,CH₂CH₂CH₂CHO, C(O)CH₃, or CH₂C(O)CH₃; and R² is H, CH₃, CH₂CH₃,CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅, CHO, CHO, CH₂CHO, CH₂CH₂CHO,CH₂CH₂CH₂CHO, C(O)CH₃, or CH₂C(O)CH₃.

In several embodiments, the polymerization precursor may include one of:(i) one or more of: toluene diisocyanate, methylene diphenyldiisocyanate, 1,6-hexamethylene diisocyanate,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and4,4′-diisocyanato dicyclohexylmethane; (ii) one or more of: a petroleumpolyol, a bio-based polyester polyol, a foam forming surfactant, atrialkylamine, a polyalkylamino alkyl ether, an alkanol amine, apromoter, an antioxidant, a flame-retardant, an ultraviolet lightstabilizer, a pigment, a dye, and a plasticizer; (iii) one or more of:formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde,valeraldehyde, glutaraldehyde glyoxal, benzaldehyde, propane-1,3-dial,butane-1,4-dial, acetone, 2-butanone, 2-pentanone, 3-pentanone,butane-2,3-dione, and pentane-2,4-dione; (iv) a phenol compound, a ureaor a substituted urea, and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal,benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone,2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione; (v) aurea or substituted urea and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal,benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone,2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione; and(vi) a phenol-formaldehyde resin.

In various embodiments, the method may include contacting aviscosity-reducing modifier to one or more of the alkoxylated bio-oiland the polymerization precursor mixture. The polymerization precursormixture may include a phenol compound and one or more of an aldehyde anda ketone. The aldehyde may include one or more of: formaldehyde,acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde,benzaldehyde, glyoxal, propane-1,3-dial, butane-1,4-dial, andglutaraldehyde. The ketone may include one or more of: acetone,2-butanone, 2-pentanone, 3-pentanone, butane-2,3-dione, andpentane-2,4-dione. The phenol compound and one or more of the aldehydeand the ketone may react to form a crosslinking agent including a phenolsubstituted at an aryl carbon with one or more of: —RCHOH and —CR¹R²OH.R may be H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅, CHO, CH₂CHO,CH₂CH₂CHO, or CH₂CH₂CH₂CHO. R may be CH₃, CH₂CH₃, CH₂CH₂CH₃,CH₂CH₂CH₂CH₃, C₆H₅, C(O)CH₃, or CH₂C(O)CH₃; and R² is CH₃, CH₂CH₃,CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅, C(O)CH₃, or CH₂C(O)CH₃.

In some embodiments, the copolymer may include one or more of: aphenol-formaldehyde resin; a phenol-urea-formaldehyde resin, aurea-formaldehyde resin, a polyester, and a polyurethane.

In various embodiments, a copolymer composition is provided. Thecopolymer composition may include a copolymer including: an alkoxylatedbio-oil unit, the alkoxylated bio-oil unit derived from an alkoxylatedbio-oil composition including an alkoxylated bio-oil; and across-linking unit, the cross-linking unit derived from a crosslinkingreagent and effective to crosslink more than one alkoxylated bio-oilunit to form the copolymer.

The copolymer composition may include any aspect of the copolymercomposition described herein. For example, in some embodiments, thealkoxylated bio-oil unit may be characterized by one or more of: derivedfrom a dewatered bio-oil; derived from a direct alkoxylation of adewatered bio-oil; derived from alkoxylation with one or more of anepoxide reagent and a cyclic carbonate; and derived from bio-oil beingproduced by pyrolysis or catalytic pyrolysis of a biomass. The copolymermay include one or more of: a polyurethane, a polyester, aphenol-formaldehyde resin, a phenol-urea-formaldehyde resin, aphenol-formaldehyde resin, a phenol-formaldehyde-urea resin, and aurea-formaldehyde resin. The cross-linking unit derived from acrosslinking reagent may be characterized by one of: (i) derived from acrosslinking reagent including at least two isocyanate groups; (ii)including at least two carboxylic acid derivative groups, the at leasttwo carboxylic acid derivative groups including one or more of: acarboxylic acid, an ester, an acyl halide, an anhydride, and a cyclicanhydride; (iii) including a phenol compound substituted at an arylcarbon with a 1-hydroxyalkyl group; (iv) derived from a product of an insitu reaction of a phenol compound and one or more of: formaldehyde,acetaldehyde, propionaldehyde, butryaldehyde, valeraldehyde,benzaldehyde, glyoxal, propane-1,3-dial, butane-1,4-dial, andglutaraldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone,butane-2,3-dione, and pentane-2,4-dione; (v) derived from a product ofan in situ reaction of a phenol compound, urea or a substituted urea,and one or more of: formaldehyde, acetaldehyde, propionaldehyde,butryaldehyde, valeraldehyde, benzaldehyde, glyoxal, propane-1,3-dial,butane-1,4-dial, and glutaraldehyde, acetone, 2-butanone, 2-pentanone,3-pentanone, butane-2,3-dione, and pentane-2,4-dione; and (vi) derivedfrom a product of an in situ reaction of urea or a substituted urea, andone or more of: formaldehyde, acetaldehyde, propionaldehyde,butryaldehyde, valeraldehyde, benzaldehyde, glyoxal, propane-1,3-dial,butane-1,4-dial, and glutaraldehyde, acetone, 2-butanone, 2-pentanone,3-pentanone, butane-2,3-dione, and pentane-2,4-dione. The copolymercomposition of claim may be configured as one or more of: a foam, aspray foam, an extrusion, an injection molding, a coating, an adhesive,an elastomer, a foundry resin, a sealant, a casting, a fiber, a pottingcompound, a reaction injection molded (RIM) plastic, a microcellularelastomer or foam, and an integral skin foam.

EXAMPLES

The following examples and results are tabulated in FIGS. 2-5 .

Example 1: Alkoxylation of Dewatered Lite Bio-Oil and Copolymerizationwith Lupranate

A sample of lite bio-oil (KF=35.3%) was placed onto a rotary evaporatorat 70° C. under 25 mmHg reduced pressure for 2 h. The resultingdewatered lite bio-oil had a KF value (Karl Fischer) of 3.02%. A 300 mLautoclave was charged with the dewatered lite bio-oil (110.56 g),propylene oxide (47.58 g, 30 wt %), and potassium hydroxide (0.49 g,0.44 wt %). The mixture was stirred and heated at 130° C. for 4 h, andthe resulting alkoxylated lite bio-oil was transferred to a jar. Thealkoxylated lite bio-oil exhibited a viscosity of 3.2 P. The alkoxylatedlite bio-oil exhibited an acid value (AV) of 3.1 and a hydroxyl value(HV) of 584, as determined by a standard phosphorus (³¹P) nuclearmagnetic resonance (NMR) technique.

The alkoxylated lite bio-oil was mixed with a petroleum polyol (JEFFOL®SG-360, Huntsman), water, surfactant (DABCO® DC193, Air Products andChemicals, Inc., Allentown Pa.) and amine (DABCO® 33LV), and promoter(NIAX*™ A1, Momentive Performance Materials Inc., Columbus, Ohio) andstirred at 3100 rpm for 1 min. LUPRANATE® M20S (BASF, Florham Park,N.J.) was added and the mixture was stirred at 3100 rpm for 6 sec. Themixture was poured into an open cake box (6″×6″×3″). The resultingalkoxylated lite bio-oil polyurethane foam did not rise over 1 in. Thisobservation was likely due to the larger amounts of water present in thefeed causing the production of polypropylene glycol.

Example 2: Alkoxylation of Dewatered Heavy+Lite Bio-Oil andCopolymerization with Lupranate

A sample of pyrolytic bio-oil including lite and heavy bio-oil fractionsrepresenting a full composition bio-oil (KF=29.3%) was placed onto arotary evaporator at 70° C. under 25 mmHg reduced pressure for 2 h. Theresulting dewatered lite bio-oil had a KF value (Karl Fischer) of 1.86%.A 300 mL autoclave was charged with the dewatered full compositionbio-oil (126.23 g), propylene oxide (54.35, 30 wt %), and potassiumhydroxide (0.54 g, 0.43 wt %). The mixture was stirred and heated at130° C. for 4 h, and the resulting alkoxylated full composition bio-oilwas transferred to a jar. The alkoxylated full composition bio-oil had aviscosity of 12 P. The alkoxylated full composition bio-oil exhibited anacid value (AV) of 0 and a hydroxyl value (HV) of 507, as determined bya standard phosphorus (³¹P) nuclear magnetic resonance (NMR) technique.

The alkoxylated full composition bio-oil was mixed with a petroleumpolyol (JEFFOL® SG-360, Huntsman, The Woodlands, Tex.), water,surfactant (DABCO® DC193, Air Products and Chemicals, Inc., AllentownPa.) and amine (DABCO® 33LV), and promoter (NIAX*™ A1, MomentivePerformance Materials Inc., Columbus, Ohio) and stirred at 3100 rpm for1 min. LUPRANATE® M20S (BASF, Florham Park, N.J.) was added and themixture was stirred at 3100 rpm for 6 sec. The mixture was poured intoan open cake box (6″×6″×3″). The resulting alkoxylated full compositionbio-oil polyurethane provided a rigid foam and exhibited a compressionstrength of 100 psi and a density of 1.63.

Example 3: Alkoxylation of Dewatered Heavy Bio-Oil and Copolymerizationwith Lupranate

A sample of heavy bio-oil (KF=11.3%) was placed onto a rotary evaporatorat 70° C. under 25 mmHg reduced pressure for 2 h. The resultingdewatered lite bio-oil had a KF value (Karl Fischer) of 1.55%. A 300 mLautoclave was charged with the dewatered heavy bio-oil (103.30 g),propylene oxide (45.35, 30 wt %), and potassium hydroxide (0.48 g, 0.46wt %). The mixture was stirred and heated at 130° C. for 4 h, and theresulting alkoxylated full composition bio-oil was transferred to ajar.The alkoxylated heavy bio-oil exhibited a viscosity of 49 P. Thealkoxylated heavy bio-oil exhibited an acid value (AV) of 0 and ahydroxyl value (HV) of 415, as determined by a standard phosphorus (³¹P)nuclear magnetic resonance (NMR) technique.

The alkoxylated heavy bio-oil was mixed with a petroleum polyol (JEFFOL®SG-360, Huntsman, The Woodlands, Tex.), water, surfactant (DABCO® DC193,Air Products and Chemicals, Inc., Allentown Pa.) and amine (DABCO®33LV), and promoter (NIAX*™ A1, Momentive Performance Materials Inc.,Columbus, Ohio) and stirred at 3100 rpm for 1 min. LUPRANATE® M20S(BASF, Florham Park, N.J.) was added and the mixture was stirred at 3100rpm for 6 sec. The mixture was poured into an open cake box (6″×6″×3″).The resulting alkoxylated heavy bio-oil polyurethane foam with acompression strength of 175 psi and a density of 1.85. A correcteddeviation from a standard was determined to be 66 psi. The correcteddeviation from a standard is the compressive strength difference fromdensity corrected reference foam. The correction deviation from astandard may be calculated by taking the sample foam compressivestrength and subtracting the reference foam compressive strength at thesample foam density as determined by linear extrapolation (see FIG. 6for reference foam densities vs compressive strength correlations).

Example 4: Alkoxylation of Dewatered Bio-Oil Derived from PyrolizedBiomass and Copolymerizaton with Luprinate

A sample of bio-oil (KF=10.5%) was placed onto a rotary evaporator at90° C. under 25 mmHg reduced pressure for 4 h. A 300 mL autoclave wascharged with the dewatered bio-oil (130.01 g), propylene oxide (55.97,30 wt %), and potassium hydroxide (0.60 g, 0.46 wt %). The mixture wasstirred and heated at 130° C. for 4 h, and the resulting alkoxylatedfull composition bio-oil was transferred to a jar. The alkoxylatedbio-oil exhibited a viscosity of 342 P. The alkoxylated bio-oilexhibited an acid value (AV) of 0 and a hydroxyl value (HV) of 242, asdetermined by a standard phosphorus (³¹P) nuclear magnetic resonance(NMR) technique.

The alkoxylated bio-oil was mixed with a petroleum polyol (JEFFOL®SG-360, Huntsman, The Woodlands, Tex.), water, surfactant (DABCO® DC193,Air Products and Chemicals, Inc., Allentown Pa.) and amine (DABCO®33LV), and promoter (NIAX*™ A1, Momentive Performance Materials Inc.,Columbus, Ohio) and stirred at 3100 rpm for 1 min. LUPRANATE® M20S(BASF, Florham Park, N.J.) was added and the mixture was stirred at 3100rpm for 6 sec. The mixture was poured into an open cake box (6″×6″×3″).The resulting alkoxylated bio-oil polyurethane foam with a compressionstrength of 213 psi and a density of 2.43. A corrected deviation from astandard was determined to be 58 psi. The corrected deviation from astandard is the compressive strength difference from density correctedreference foam. The correction deviation from a standard may becalculated by taking the sample foam compressive strength andsubtracting the reference foam compressive strength at the sample foamdensity as determined by linear extrapolation (see FIG. 6 for referencefoam densities vs compressive strength correlations).

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” To the extent that the term“selectively” is used in the specification or the claims, it is intendedto refer to a condition of a component wherein a user of the apparatusmay activate or deactivate the feature or function of the component asis necessary or desired in use of the apparatus. To the extent that theterm “operatively connected” is used in the specification or the claims,it is intended to mean that the identified components are connected in away to perform a designated function. To the extent that the term“substantially” is used in the specification or the claims, it isintended to mean that the identified components have the relation orqualities indicated with degree of error as would be acceptable in thesubject industry.

As used in the specification and the claims, the singular forms “a,”“an,” and “the” include the plural unless the singular is expresslyspecified. For example, reference to “a compound” may include a mixtureof two or more compounds, as well as a single compound.

As used herein, the term “about” in conjunction with a number isintended to include ±10% of the number. In other words, “about 10” maymean from 9 to 11.

As used herein, the terms “optional” and “optionally” mean that thesubsequently described circumstance may or may not occur, so that thedescription includes instances where the circumstance occurs andinstances where it does not.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group. As will beunderstood by one skilled in the art, for any and all purposes, such asin terms of providing a written description, all ranges disclosed hereinalso encompass any and all possible sub-ranges and combinations ofsub-ranges thereof. Any listed range can be easily recognized assufficiently describing and enabling the same range being broken downinto at least equal halves, thirds, quarters, fifths, tenths, and thelike. As a non-limiting example, each range discussed herein can bereadily broken down into a lower third, middle third and upper third,and the like. As will also be understood by one skilled in the art alllanguage such as “up to,” “at least,” “greater than,” “less than,”include the number recited and refer to ranges which can be subsequentlybroken down into sub-ranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember. For example, a group having 1-3 cells refers to groups having 1,2, or 3 cells. Similarly, a group having 1-5 cells refers to groupshaving 1, 2, 3, 4, or 5 cells, and so forth. While various aspects andembodiments have been disclosed herein, other aspects and embodimentswill be apparent to those skilled in the art.

As stated above, while the present application has been illustrated bythe description of embodiments thereof, and while the embodiments havebeen described in considerable detail, it is not the intention of theapplicants to restrict or in any way limit the scope of the appendedclaims to such detail. Additional advantages and modifications willreadily appear to those skilled in the art, having the benefit of thepresent application. Therefore, the application, in its broader aspects,is not limited to the specific details, illustrative examples shown, orany apparatus referred to. Departures may be made from such details,examples, and apparatuses without departing from the spirit or scope ofthe general inventive concept.

As used herein, “substituted” refers to an organic group as definedbelow (e.g., an alkyl group) in which one or more bonds to a hydrogenatom contained therein may be replaced by a bond to non-hydrogen ornon-carbon atoms. Substituted groups also include groups in which one ormore bonds to a carbon(s) or hydrogen(s) atom may be replaced by one ormore bonds, including double or triple bonds, to a heteroatom. Asubstituted group may be substituted with one or more substituents,unless otherwise specified. In some embodiments, a substituted group maybe substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples ofsubstituent groups include: halogens (F, Cl, Br, and I); hydroxyls;alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyloxy, andheterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters;urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols;sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines;N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas;amidines; guanidines; enamines; imides; isocyanates; isothiocyanates;cyanates; thiocyanates; imines; nitro groups; or nitriles. A“per”-substituted compound or group is a compound or group having all orsubstantially all substitutable positions substituted with the indicatedsubstituent. For example, 1,6-diiodo perfluoro hexane indicates acompound of formula C₆F₁₂I₂, where all the substitutable hydrogens havebeen replaced with fluorine atoms.

Substituted ring groups such as substituted cycloalkyl, aryl,heterocyclyl and heteroaryl groups also include rings and ring systemsin which a bond to a hydrogen atom may be replaced with a bond to acarbon atom. Substituted cycloalkyl, aryl, heterocyclyl and heteroarylgroups may also be substituted with substituted or unsubstituted alkyl,alkenyl, and alkynyl groups as defined below.

Alkyl groups include straight chain and branched chain alkyl groupshaving from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or,in some examples, from 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examplesof straight chain alkyl groups include groups such as methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.Examples of branched alkyl groups include, but are not limited to,isopropyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. Representative substituted alkyl groups maybe substituted one or more times with substituents such as those listedabove and include, without limitation, haloalkyl (e.g.,trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl,dialkylaminoalkyl, alkoxyalkyl, or carboxyalkyl.

Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups havingfrom 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Exemplary monocycliccycloalkyl groups include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.In some embodiments, the cycloalkyl group has 3 to 8 ring members,whereas in other embodiments, the number of ring carbon atoms rangesfrom 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems includeboth bridged cycloalkyl groups and fused rings, such as, but not limitedto, bicyclo[2.1.1]hexane, adamantyl, or decalinyl. Substitutedcycloalkyl groups may be substituted one or more times with non-hydrogenand non-carbon groups as defined above. However, substituted cycloalkylgroups also include rings that may be substituted with straight orbranched chain alkyl groups as defined above. Representative substitutedcycloalkyl groups may be mono-substituted or substituted more than once,such as, but not limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstitutedcyclohexyl groups, which may be substituted with substituents such asthose listed above.

Aryl groups may be cyclic aromatic hydrocarbons that do not containheteroatoms. Aryl groups herein include monocyclic, bicyclic andtricyclic ring systems. Aryl groups include, but are not limited to,phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl,anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. In someembodiments, aryl groups contain 6-14 carbons, and in others from 6 to12 or even 6-10 carbon atoms in the ring portions of the groups. In someembodiments, the aryl groups may be phenyl or naphthyl. Although thephrase “aryl groups” may include groups containing fused rings, such asfused aromatic-aliphatic ring systems (e.g., indanyl ortetrahydronaphthyl), “aryl groups” does not include aryl groups thathave other groups, such as alkyl or halo groups, bonded to one of thering members. Rather, groups such as tolyl may be referred to assubstituted aryl groups. Representative substituted aryl groups may bemono-substituted or substituted more than once. For example,monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-,5-, or 6-substituted phenyl or naphthyl, which may be substituted withsubstituents such as those above.

Aralkyl groups may be alkyl groups as defined above in which a hydrogenor carbon bond of an alkyl group may be replaced with a bond to an arylgroup as defined above. In some embodiments, aralkyl groups contain 7 to16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms.Substituted aralkyl groups may be substituted at the alkyl, the aryl orboth the alkyl and aryl portions of the group. Representative aralkylgroups include but are not limited to benzyl and phenethyl groups andfused (cycloalkylaryl)alkyl groups such as 4-indanylethyl. Substitutedaralkyls may be substituted one or more times with substituents aslisted above.

Groups described herein having two or more points of attachment (e.g.,divalent, trivalent, or polyvalent) within the compound of thetechnology may be designated by use of the suffix, “ene.” For example,divalent alkyl groups may be alkylene groups, divalent aryl groups maybe arylene groups, divalent heteroaryl groups may be heteroarylenegroups, and so forth. In particular, certain polymers may be describedby use of the suffix “ene” in conjunction with a term describing thepolymer repeat unit.

Alkoxy groups may be hydroxyl groups (—OH) in which the bond to thehydrogen atom may be replaced by a bond to a carbon atom of asubstituted or unsubstituted alkyl group as defined above. Examples oflinear alkoxy groups include, but are not limited to, methoxy, ethoxy,propoxy, butoxy, pentoxy, or hexoxy. Examples of branched alkoxy groupsinclude, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy,isopentoxy, or isohexoxy. Examples of cycloalkoxy groups include, butare not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, orcyclohexyloxy. Representative substituted alkoxy groups may besubstituted one or more times with substituents such as those listedabove.

The term “amine” (or “amino”), as used herein, refers to NR₅R₆ groups,wherein R₅ and R₆ may be independently hydrogen, or a substituted orunsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl,heterocyclylalkyl or heterocyclyl group as defined herein. In someembodiments, the amine may be alkylamino, dialkylamino, arylamino, oralkylarylamino. In other embodiments, the amine may be NH₂, methylamino,dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino,phenylamino, or benzylamino. The term “alkylamino” may be defined asNR₇R₈, wherein at least one of R₇ and R₈ may be alkyl and the other maybe alkyl or hydrogen. The term “arylamino” may be defined as NR⁹R¹⁰,wherein at least one of R⁹ and R¹⁰ may be aryl and the other may be arylor hydrogen.

The term “halogen” or “halo,” as used herein, refers to bromine,chlorine, fluorine, or iodine. In some embodiments, the halogen may befluorine. In other embodiments, the halogen may be chlorine or bromine.

The various aspects and embodiments disclosed herein are for purposes ofillustration and are not intended to be limiting, with the true scopeand spirit being indicated by the following claims.

The invention claimed is:
 1. A method for preparing an alkoxylatedbio-oil composition, the method comprising: providing a dewateredbio-oil, wherein the dewatered bio-oil is obtained by dewatering abio-oil, wherein the dewatered bio-oil is obtained from pyrolysis ofwood or other lignocellulosic-containing biomass; and contacting thedewatered bio-oil with an alkoxylation reagent consisting one of: anepoxide and a cyclic carbonate in a presence of a promoter underreaction conditions effective to form an alkoxylated bio-oil having ahydroxyl value of at least 415, wherein the alkoxylated bio-oil isderived from direct alkoxylation of the dewatered bio-oil using thealkoxylation reagent.
 2. The method of claim 1, further comprisingdewatering a bio-oil to produce the dewatered by one or more of:distillation, vacuum distillation, azeotropic distillation, evaporation,salting out, freeze drying, adsorption, desiccation, and centrifugation.3. The method of claim 1, wherein the alkoxylated bio-oil is reactedwith a polymerization precursor mixture under reaction conditionseffective to form a copolymer composition, wherein a cross-linking agentcomprised in the precursor crosslinks the alkoxylated bio-oil to formthe copolymer.
 4. The method of claim 1, the alkoxylation reagentcomprising one or more of: ethylene oxide optionally substituted withone or more of a linear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkylgroup, and a C₄-C₁₀ aryl or heteroaryl group; ethylene carbonateoptionally substituted with one or more of a linear or branched C₁-C₆alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀ aryl or heteroaryl group;and trimethylene carbonate optionally substituted with one or more of alinear or branched C₁-C₆ alkyl, a C₃-C₆ cycloalkyl group, and a C₄-C₁₀aryl or heteroaryl group.
 5. The method of claim 1, the reactionconditions comprising one or more of: the alkoxylation reagent beingpresent in an amount greater than 5 wt % compared to an amount of thedewatered bio-oil; the presence of a promoter, comprising one of an acidand a base; the promoter being present in an amount between about 0.005wt % and 5 wt % compared to an amount of the dewatered bio-oil; areaction temperature of between about 80° C. and about 180° C.; areaction pressure in pounds per square inch of between about 0 and about600; the dewatered bio-oil comprising a pyrolytic bio-oil or a catalyticpyrolytic bio-oil; less than about 30 wt % water compared to thedewatered bio-oil; and production of a free alkylene glycol byproduct atless than about 40 wt % compared to the dewatered bio-oil.
 6. The methodof claim 1, further comprising: contacting the dewatered bio-oil with apromoter; allowing the dewatered bio-oil and the promotor to react for aperiod of time prior to contacting the dewatered bio-oil with thealkoxylation reagent; optionally heating the dewatered bio-oil and thepromoter, optionally under reduced pressure, for a period of time priorto contacting the dewatered bio-oil with the alkoxylation reagent, thepromoter comprising an alkali metal hydroxide; and optionally condensinga water vapor into a container separate from the dewatered bio-oil andthe promoter prior to contacting the dewatered bio-oil with thealkoxylation reagent.
 7. An alkoxylated bio-oil composition comprising:an alkoxylated bio-oil having a hydroxyl value of at least 415, thealkoxylated bio-oil derived from direct alkoxylation of a dewateredbio-oil using an alkoxylation reagent consisting one of: an epoxide anda cyclic carbonate in a presence of a promoter, the dewatered bio-oil isobtained by dewatering a bio-oil, wherein the bio-oil is obtained fromthe pyrolysis of wood or other lignocellulosic-containing biomass; andan amount of a free alkylene glycol of less than about 40 wt % comparedto an amount of the alkoxylated bio-oil.
 8. The alkoxylated bio-oilcomposition of claim 7, the alkoxylated bio-oil characterized by one ormore of: comprising at least one polyalkylene glycol unit covalentlybound to one or more of an acid, an alcohol, and a phenol functionalityoriginated in the dewatered bio-oil; the dewatered bio-oil comprising apyrolytic bio-oil or a catalytic pyrolytic bio-oil; and in comparison tothe dewatered bio-oil, by one or more of: a reduced viscosity, anincreased molecular weight, a lower gel permeation chromatographyretention time, and a reduced hydroxyl value.
 9. The method of claim 1,wherein the alkoxylated bio-oil characterized by one or more of:comprising at least one polyalkylene glycol unit covalently bound to oneor more of an acid, an alcohol, and a phenol functionality originated inthe dewatered bio-oil; and in comparison to the dewatered bio-oil, byone or more of: a reduced viscosity, an increased molecular weight, alower gel permeation chromatography retention time.
 10. The method ofclaim 1, wherein the dewatered bio-oil comprising water in less thanabout 3 wt % compared to the amount of dewatered bio-oil.
 11. The methodof claim 1, the alkoxylated bio-oil produced from the dewatered bio-oil,the dewatered bio-oil comprising water of less than about 30 wt %. 12.The method of claim 1, wherein the alkoxylated bio-oil has a hydroxylvalue from 415 to
 584. 13. The method of claim 3, wherein thecrosslinking reagent comprising one of: at least two isocyanate groups;at least two carboxylic acid derivative groups; one or more of: acarboxylic acid, an ester, a acyl halide, a cyclic anhydride, and ananhydride; and a phenol compound substituted at an aryl carbon with atleast one —CR′R²OH, wherein: le is H, CH₃, CH₂CH₃, CH₂CH₂CH₃,CH₂CH₂CH₂CH₃, C₆H₅, CHO, CHO, CH₂CHO, CH₂CH₂CHO, CH₂CH₂CH₂CHO, C(O)CH₃,or CH₂C(O)CH₃; and R² is H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, C₆H₅,CHO, CHO, CH₂CHO, CH₂CH₂CHO, CH₂CH₂CH₂CHO, C(O)CH₃, or CH₂C(O)CH₃. 14.The method of claim 3, the polymerization precursor comprising one of:one or more of: toluene diisocyanate, methylene diphenyl diisocyanate,1,6-hexamethylene diisocyanate,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and4,4′-diisocyanato dicyclohexylmethane; (ii) one or more of: a petroleumpolyol, a bio-based polyester polyol, a foam forming surfactant, atrialkylamine, a polyalkylamino alkyl ether, an alkanol amine, apromoter, an antioxidant, a flame-retardant, an ultraviolet lightstabilizer, a pigment, a dye, and a plasticizer; (iii) one or more of:formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde,valeraldehyde, glutaraldehyde glyoxal, benzaldehyde, propane-1,3-dial,butane-1,4-dial, acetone, 2-butanone, 2-pentanone, 3-pentanone,butane-2,3-dione, and pentane-2,4-dione; (iv) a phenol compound, a ureaor a substituted urea, and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal,benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone,2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione; (v) aurea or substituted urea and one or more of: formaldehyde, acetaldehyde,propionaldehyde, butryaldehyde, valeraldehyde, glutaraldehyde glyoxal,benzaldehyde, propane-1,3-dial, butane-1,4-dial, acetone, 2-butanone,2-pentanone, 3-pentanone, butane-2,3-dione, and pentane-2,4-dione; and(vi) a phenol-formaldehyde resin.
 15. The method of claim 3, wherein theforming of the copolymer further comprising contacting aviscosity-reducing modifier to one or more of the alkoxylated bio-oiland the polymerization precursor mixture.
 16. The alkoxylated bio-oilcomposition of claim 7, wherein the alkoxylated bio-oil characterized byone or more of: comprising at least one polyalkylene glycol unitcovalently bound to one or more of an acid, an alcohol, and a phenolfunctionality originated in the dewatered bio-oil; and in comparison tothe dewatered bio-oil, by one or more of: a reduced viscosity, anincreased molecular weight, a lower gel permeation chromatographyretention time.
 17. The alkoxylated bio-oil composition of claim 7,wherein the dewatered bio-oil comprising water in less than about 3 wt %compared to the amount of dewatered bio-oil.
 18. The alkoxylated bio-oilcomposition of claim 7, the alkoxylated bio-oil produced from thedewatered bio-oil, the dewatered bio-oil comprising water of less thanabout 30 wt %.
 19. The alkoxylated bio-oil composition of claim 7,wherein the alkoxylated bio-oil has a hydroxyl value from 415 to 584.